U.S. patent application number 16/647924 was filed with the patent office on 2020-08-20 for melt polymerization method for polyetherimides.
The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to Javier Nieves Remacha, Juan Justino Rodriguez Ordonez, Bernabe Quevedo Sanchez, Nitin Vilas Tople.
Application Number | 20200262977 16/647924 |
Document ID | 20200262977 / US20200262977 |
Family ID | 1000004840658 |
Filed Date | 2020-08-20 |
Patent Application | download [pdf] |
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United States Patent
Application |
20200262977 |
Kind Code |
A1 |
Tople; Nitin Vilas ; et
al. |
August 20, 2020 |
MELT POLYMERIZATION METHOD FOR POLYETHERIMIDES
Abstract
A method of making a polyetherimide includes forming a monomer
mixture comprising a bis(ether anhydride), a diamine and a volatile
organic solvent; removing the volatile organic solvent to form a
particulate solid; and melt polymerizing the particulate solid at a
temperature 50 to 225.degree. C. greater than the glass transition
temperature of the polyetherimide in a single melt mixing device.
The polyetherimide has an anhydride-amine stoichiometry and the
standard deviation of anhydride-amine stoichiometry is less than
0.4 mol %.
Inventors: |
Tople; Nitin Vilas;
(Evansville, IN) ; Quevedo Sanchez; Bernabe;
(Cartagena, ES) ; Ordonez; Juan Justino Rodriguez;
(San Javier, ES) ; Nieves Remacha; Javier;
(Madrid, ES) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
Bergen op Zoom |
|
NL |
|
|
Family ID: |
1000004840658 |
Appl. No.: |
16/647924 |
Filed: |
September 19, 2018 |
PCT Filed: |
September 19, 2018 |
PCT NO: |
PCT/US2018/051695 |
371 Date: |
March 17, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 73/1053 20130101;
C08G 73/1032 20130101 |
International
Class: |
C08G 73/10 20060101
C08G073/10 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 20, 2017 |
EP |
17382617.3 |
Claims
1. A method of making a polyetherimide comprises forming a monomer
mixture comprising a bis(ether anhydride), a diamine and a volatile
organic solvent; removing the volatile organic solvent to form a
particulate solid; and melt polymerizing the particulate solid at a
temperature of 50 to 225.degree. C. higher than the glass
transition temperature of the polyetherimide in a single melt
mixing device to produce a polyetherimide having an anhydride-amine
stoichiometry and the standard deviation of anhydride-amine
stoichiometry is less than 0.4 mol %.
2. The method of claim 1, wherein the monomer mixture is formed by
combining a bis(ether anhydride) mixture and a diamine mixture,
wherein the bis(ether anhydride) mixture comprises the bis(ether
anhydride) and the volatile organic solvent and the diamine mixture
comprises the diamine and the volatile organic solvent.
3. The method of claim 2, wherein the bis(ether anhydride) mixture
further comprises a chain stopper.
4. The method of claim 2, wherein the diamine mixture further
comprises a chain stopper.
5. The method of claim 1, wherein at least a portion of the melt
polymerization is conducted at a pressure below atmospheric
pressure (760 mm Hg or 101,325 Pa).
6. The method of claim 1, wherein an excess of bis(ether anhydride)
relative to the diamine is used to produce a polyetherimide having
an excess of anhydride groups relative to the amount of amine
groups.
7. The method of claim 1, wherein the volatile organic solvent
comprises dichloromethane, chloroform, or a combination of the
foregoing.
8. The method of claim 1, wherein melt polymerizing occurs at a
temperature 50 to 150.degree. C. greater than the glass transition
temperature of the polyetherimide.
9. The method of claim 1, wherein at least a portion of the melt
polymerization is conducted at a pressure less than or equal to
5,000 Pa.
10. The method of claim 1, wherein the bis(ether anhydride)
comprises 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane
dianhydride.
11. The method of claim 1, wherein the diamine comprises
m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl
sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl
sulfone, or a combination comprising at least one of the
foregoing.
12. The method of claim 1, wherein the particulate solid has a
solvent content less than or equal to 1000 ppm.
13. A melt polymerized polyetherimide having anhydride-amine
stoichiometry wherein the standard deviation of anhydride-amine
stoichiometry is less than 0.4 mol % and a solvent content less
than 50 ppm.
14. The polyetherimide of claim 13, wherein the polyetherimide has
an anhydride-amine stoichiometry of -1 to 2.5 mol %.
15. The polyetherimide of claim 13, wherein the polyetherimide has
a chlorine content less than or equal to 50 ppm.
16. The polyetherimide of claim 13, wherein the polyetherimide has
a change in melt viscosity of less than or equal to 50% after being
maintained for 30 minutes at 390.degree. C. wherein melt viscosity
is determined by ASTM D4440.
17. The polyetherimide of claim 13 comprising structural units
derived from 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane
dianhydride and one or more diamines comprising m-phenylenediamine,
p-phenylenediamine, 4,4'-diaminodiphenyl sulfone,
3,4'-diaminodiphenyl sulfone, or 3,3'-diaminodiphenyl sulfone.
Description
BACKGROUND
[0001] Polyetherimides can be made by solution polymerization
methods or by melt polymerization methods. Melt polymerization
methods offer advantages but these advantages have been outweighed
by difficulties associated with both the method and the polymer
produced by the method. Further improvements to melt polymerization
methods are needed.
BRIEF DESCRIPTION
[0002] Disclosed herein is a method of making a polyetherimide
comprising forming a monomer mixture comprising a bis(ether
anhydride), a diamine and a volatile organic solvent; removing the
volatile organic solvent to form a particulate solid; and melt
polymerizing the particulate solid at a temperature 50 to
225.degree. C. greater than the glass transition temperature of the
polyetherimide in a single melt mixing device. The polyetherimide
has an anhydride-amine stoichiometry and the standard deviation of
anhydride-amine stoichiometry is less than 0.4 mol %. The
polyetherimide also has a solvent content less than 50 ppm. The
polyetherimide may have a chlorine content less than or equal to 50
ppm.
[0003] Also disclosed herein is a method of making a polyetherimide
comprising forming a monomer mixture comprising
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, a
volatile organic solvent; and a diamine comprising
m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl
sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl
sulfone, or a combination comprising at least one of the foregoing;
removing the volatile organic solvent to form a particulate solid;
and melt polymerizing the particulate solid at a temperature 50 to
225.degree. C. greater than the glass transition temperature of the
polyetherimide in a single melt mixing device. The polyetherimide
has an anhydride-amine stoichiometry and the standard deviation of
anhydride-amine stoichiometry is less than 0.4 mol %. The
polyetherimide also has a solvent content less than 50 ppm. The
polyetherimide may have a chlorine content less than or equal to 50
ppm.
[0004] Additionally disclosed is a melt polymerized polyetherimide
having anhydride-amine stoichiometry wherein the standard deviation
of anhydride-amine stoichiometry is less than 0.4 mol %. The
polyetherimide also has a solvent content less than 50 ppm. The
polyetherimide may have a chlorine content less than or equal to 50
ppm.
[0005] The above described and other features are exemplified by
the following figures and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The following figures are exemplary embodiments wherein the
like elements are numbered alike.
[0007] FIGS. 1-6 show reaction conditions and data from the
Examples.
DETAILED DESCRIPTION
[0008] Melt polymerization methods may experience a "cement stage"
in early stages of polymerization. The "cement stage" is
characterized by extremely hard polymer of very high molecular
weight. The presence of the "cement stage" can lead to non-steady
operations and equipment failure.
[0009] It was discovered that the "cement stage" could be avoided
by forming a mixture of the aromatic bis(ether anhydride), diamine
and optional chain stopper using a volatile organic solvent. The
solvent is then removed from the mixture to form a particulate
solid. The particulate solid comprises a plurality of particles.
The particulate solid is then melt polymerized. Without being bound
by theory it is believed that by melt polymerizing the particulate
solid the "cement stage" is avoided. As demonstrated in the
Examples the "cement stage" appears to be the result of a
non-homogenous distribution of monomers during melt
polymerization.
[0010] In some embodiments the aromatic bis(ether anhydride) is
combined with a volatile organic solvent to form a first mixture.
The diamine is combined with a volatile organic solvent to form a
second solution. A chain stopper, if used, may be with a volatile
organic solvent to form a third mixture or combined with the
aromatic bis(ether anhydride), with the diamine, with both. The
volatile organic solvent used in the first, second and optional
third mixture may be the same or different. For example, the first
and third mixture may employ one volatile organic solvent while the
second mixture employs a different volatile organic solvent. Any of
the above mixtures with a volatile organic solvent may be a slurry
or a solution.
[0011] Volatile organic solvents include those having a boiling
point less than or equal to 65.degree. C. at atmospheric pressure.
Exemplary volatile organic solvents include dichloromethane, and
chloroform and combinations of the foregoing.
[0012] As used herein the term "mixture" refers to a liquid mixture
in which the minor component by weight (the bis(ether anhydride),
diamine and/or the chain stopper) is uniformly distributed within
the major component by weight (the solvent).
[0013] The first mixture, second mixture and, if used, the third
mixture are combined to form the final mixture. In some embodiments
the combination of the first, second and optional third mixtures
may result in an exothermic reaction. The volatile organic
solvent(s) is then removed from the final mixture to form a
particulate solid. The particulate solid may have a solvent content
of less than or equal to 1000 ppm, or less than or equal to 100
ppm. The solvent content of the solid may be determined by HPLC
analysis.
[0014] The particulate solid is melt polymerized at a temperature
50 to 225.degree. C., or 50 to 150.degree. C. greater than the
glass transition temperature of the polyetherimide in a single melt
mixing device. In some embodiments melt polymerization occurs at a
temperature of 300 to 450.degree. C. Melt polymerization occurs in
a single melt mixing device.
[0015] In some embodiments at least a portion of the melt
polymerization is conducted at a pressure below atmospheric
pressure (760 mm Hg or 101,325 Pa). In particular, the pressure may
be less than or equal to 50,000 Pa, less than or equal to 25,000
Pa, less than or equal to 10,000 Pa, less than or equal to 5,000
Pa, or less than or equal to 1,000 Pa. In some embodiments the
pressure is reduced for the final 50%, 35%, 25%, or 10% of the
polymerization time. In some embodiments the pressure is reduced
for the entire polymerization. In some embodiments the pressure is
reduced once the reaction mixture has a weight average molecular
weight that is greater than or equal to 20%, or greater than or
equal to 60%, or greater than or equal to 90% of the weight average
molecular weight of the polyetherimide.
[0016] The melt polymerization can be performed in an extruder,
agitated thin film evaporator, large volume processor, mechanically
agitated reactor or other melt mixing device. The aromatic
bis(ether anhydride) and the diamine are present in amounts
sufficient to obtain an anhydride-amine ratio of 0.99 to 1.025. The
polymerization occurs for the time necessary to achieve the desired
molecular weight and desired melt stability. The melt mixing device
is vented to allow for removal of the water of reaction.
[0017] Polyetherimides comprise more than 1, for example 2 to 1000,
or 5 to 500, or 10 to 100 structural units of formula (1)
##STR00001##
[0018] wherein each R is independently the same or different, and
is a substituted or unsubstituted divalent organic group, such as a
substituted or unsubstituted C.sub.6-20 aromatic hydrocarbon group,
a substituted or unsubstituted straight or branched chain
C.sub.4-20 alkylene group, a substituted or unsubstituted C.sub.3-8
cycloalkylene group, in particular a halogenated derivative of any
of the foregoing. In some embodiments R is divalent group of one or
more of the following formulas (2)
##STR00002##
wherein Q.sup.1 is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, --C.sub.yH.sub.2y-- wherein y is an integer from 1
to 5 or a halogenated derivative thereof (which includes
perfluoroalkylene groups), or --(C.sub.6H.sub.10).sub.z-- wherein z
is an integer from 1 to 4. In some embodiments R is m-phenylene,
p-phenylene, or a diarylene sulfone, in particular
bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone,
bis(3,3'-phenylene)sulfone, or a combination comprising at least
one of the foregoing. In some embodiments, at least 10 mole percent
or at least 50 mole percent of the R groups contain sulfone groups,
and in other embodiments no R groups contain sulfone groups.
[0019] Further in formula (1), T is --O-- or a group of the formula
--O--Z--O-- wherein the divalent bonds of the --O-- or the
--O--Z--O-- group are in the 3,3', 3,4', 4,3', or the 4,4'
positions, and Z is an aromatic C.sub.6-24 monocyclic or polycyclic
moiety optionally substituted with 1 to 6 C.sub.1-8 alkyl groups, 1
to 8 halogen atoms, or a combination comprising at least one of the
foregoing, provided that the valence of Z is not exceeded.
Exemplary groups Z include groups of formula (3)
##STR00003##
wherein R.sup.a and R.sup.b are each independently the same or
different, and are a halogen atom or a monovalent C.sub.1-6 alkyl
group, for example; p and q are each independently integers of 0 to
4; c is 0 to 4; and X.sup.a is a bridging group connecting the
hydroxy-substituted aromatic groups, where the bridging group and
the hydroxy substituent of each C.sub.6 arylene group are disposed
ortho, meta, or para (specifically para) to each other on the
C.sub.6 arylene group. The bridging group X.sup.a can be a single
bond, --O--, --S--, --S(O)--, --S(O).sub.2--, --C(O)--, or a
C.sub.1-18 organic bridging group. The C.sub.1-18 organic bridging
group can be cyclic or acyclic, aromatic or non-aromatic, and can
further comprise heteroatoms such as halogens, oxygen, nitrogen,
sulfur, silicon, or phosphorous. The C.sub.1-18 organic group can
be disposed such that the C.sub.6 arylene groups connected thereto
are each connected to a common alkylidene carbon or to different
carbons of the C.sub.1-18 organic bridging group. A specific
example of a group Z is a divalent group of formula (3a)
##STR00004##
wherein Q is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, or --C.sub.yH.sub.2y-- wherein y is an integer
from 1 to 5 or a halogenated derivative thereof (including a
perfluoroalkylene group). In a specific embodiment Z is a derived
from bisphenol A, such that Q in formula (3a) is
2,2-isopropylidene.
[0020] In an embodiment in formula (1), R is m-phenylene,
p-phenylene, or a combination comprising at least one of the
foregoing, and T is --O--Z--O-- wherein Z is a divalent group of
formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a
combination comprising at least one of the foregoing, and T is
--O--Z--O wherein Z is a divalent group of formula (3a) and Q is
2,2-isopropylidene. Alternatively, the polyetherimide can be a
copolymer comprising additional structural polyetherimide units of
formula (1) wherein at least 50 mole percent (mol %) of the R
groups are bis(4,4'-phenylene)sulfone, bis(3,4'-phenylene)sulfone,
bis(3,3'-phenylene)sulfone, or a combination comprising at least
one of the foregoing and the remaining R groups are p-phenylene,
m-phenylene or a combination comprising at least one of the
foregoing; and Z is 2,2-(4-phenylene)isopropylidene, i.e., a
bisphenol A moiety.
[0021] In some embodiments, the polyetherimide is a copolymer that
optionally comprises additional structural imide units that are not
polyetherimide units, for example imide units of formula (4)
##STR00005##
wherein R is as described in formula (1) and each V is the same or
different, and is a substituted or unsubstituted C.sub.6-20
aromatic hydrocarbon group, for example a tetravalent linker of the
formulas
##STR00006##
wherein W is a single bond, --O--, --S--, --C(O)--, --SO.sub.2--,
--SO--, a C.sub.1-18 hydrocarbylene group, --P(R.sup.a)(.dbd.O)--
wherein R.sup.a is a C.sub.1-8 alkyl or C.sub.6-12 aryl, or
--C.sub.yH.sub.2y-- wherein y is an integer from 1 to 5 or a
halogenated derivative thereof (which includes perfluoroalkylene
groups). These additional structural imide units preferably
comprise less than 20 mol % of the total number of units, and more
preferably can be present in amounts of 0 to 10 mol % of the total
number of units, or 0 to 5 mol % of the total number of units, or 0
to 2 mole % of the total number of units. In some embodiments, no
additional imide units are present in the polyetherimide.
[0022] The polyetherimide is prepared by melt polymerization of an
aromatic bis(ether anhydride) of formula (5), with a diamine of
formula (6)
##STR00007##
wherein T and R are defined as described above. Copolymers of the
polyetherimides can be manufactured using a combination of an
aromatic bis(ether anhydride) of formula (5) and an additional
bis(anhydride) that is not a bis(ether anhydride), for example
pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone
dianhydride.
[0023] Illustrative examples of aromatic bis(ether anhydride)s
include 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride
(also known as bisphenol A dianhydride or BPADA),
3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone
dianhydride; 4,4'-(hexafluoroisopropylidene)diphthalic anhydride;
and 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl
sulfone dianhydride. A combination of different aromatic bis(ether
anhydride)s can be used.
[0024] Examples of diamines include 1,4-butane diamine,
1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine,
1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine,
1,12-dodecanediamine, 1,18-octadecanediamine,
3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,
4-methylnonamethylenediamine, 5-methylnonamethylenediamine,
2,5-dimethylhexamethylenediamine,
2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine,
N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine,
1,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide,
1,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane,
m-phenylenediamine (mPD), p-phenylenediamine (pPD),
2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine,
p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine,
5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,
1,5-diaminonaphthalene, bis(4-aminophenyl) methane,
bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl)
propane, 2,4-bis(p-amino-t-butyl) toluene,
bis(p-amino-t-butylphenyl) ether, bis(p-methyl-o-aminophenyl)
benzene, bis(p-methyl-o-aminopentyl) benzene, 1,
3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide,
bis-(4-aminophenyl) sulfone (also known as 4,4'-diaminodiphenyl
sulfone (DDS)), and bis(4-aminophenyl) ether. Any regioisomer of
the foregoing compounds can be used. C.sub.1-4 alkylated or
poly(C.sub.1-4)alkylated derivatives of any of the foregoing can be
used, for example a polymethylated 1,6-hexanediamine. Combinations
of these compounds can also be used. In some embodiments the
organic diamine is m-phenylenediamine, p-phenylenediamine,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
3,3'-diaminodiphenyl sulfone, or a combination comprising at least
one of the foregoing.
[0025] In some embodiments the diamine is free of a stabilizer
compound. Commercially available diamines can include stabilizer
compounds such as a reducing agent used during production of the
diamine. While intended to reduce degradation of the diamine the
presence of these stabilizers in melt polymerization can negatively
impact the melt stability of the resulting polyetherimide.
[0026] The polyetherimide may have terminal groups derived from a
chain stopper. The chain stopper may be a monoamine or a
monoanhydride. Exemplary chain stoppers include phthalic anhydride
and aniline. The amount of chain stopper can be 2 to 8 mol % based
on the total amount of the relevant functional group. For example,
when the chain stopper is a monoanhydride, the mol % of chain
stopper is defined as moles of monoanhydride/(moles of
monoanhydride+2.times. moles of bis(ether anhydride)).
[0027] The polyetherimides can have a melt index of 0.1 to 10 grams
per minute (g/min), as measured by American Society for Testing
Materials (ASTM) D1238 at 340 to 370.degree. C., using a 6.7
kilogram (kg) weight. In some embodiments, the polyetherimide has a
weight average molecular weight (Mw) of 1,000 to 150,000 grams/mole
(Dalton), as measured by gel permeation chromatography (GPC), using
polystyrene standards. In some embodiments the polyetherimide has
an Mw of 10,000 to 80,000 Daltons. Such polyetherimides typically
have an intrinsic viscosity greater than 0.2 deciliters per gram
(dl/g), or, more specifically, 0.35 to 0.7 dl/g as measured in
m-cresol at 25.degree. C.
[0028] The polyetherimide can have a glass transition temperature
of 180 to 310.degree. C. as determined by differential scanning
calorimetry (ASTM D3418).
[0029] The polyetherimide can have an anhydride-amine stoichiometry
of 2.5 to -1 mol %, or 1 to -1 mol %. Anhydride-amine stoichiometry
is defined as the mol % of anhydride--the mol % of amine groups. An
anhydride-amine stoichiometry with a negative value indicates an
excess of amine groups. Anhydride content and amine content can be
determined by Fourier transformed infrared spectroscopy or near
infrared spectroscopy.
[0030] The polyetherimide has a standard deviation of
anhydride-amine stoichiometry of less than 0.4 mol %. The standard
deviation of anhydride-amine stoichiometry is determined on the
basis of 5 samples of the polyetherimide.
[0031] The polyetherimide may have a chlorine content less than or
equal to 100 ppm, or less than or equal to 50 ppm, or, less than or
equal to 25 ppm. Chlorine content can be determined using x-ray
fluorescence spectrometry on a solid polyetherimide sample.
[0032] The polyetherimide has a solvent content less than 50 ppm,
or less than 30 ppm, or less than 10 ppm. Solvent content may be
determined by gas chromatography or liquid chromatography.
[0033] In some embodiments the polyetherimide has a change in melt
viscosity of less than or equal to 50%, less than or equal to 40%,
less than or equal to 30%, or less than or equal to 20% after being
maintained for 30 minutes at 390.degree. C. wherein melt viscosity
is determined by ASTM D4440. In some embodiments, the
polyetherimide has a change in melt viscosity of -30% to 50% after
being maintained for 30 minutes at 390.degree. C. wherein melt
viscosity is determined by ASTM D4440.
[0034] This disclosure is further illustrated by the following
examples, which are non-limiting.
EXAMPLES
Example 1
[0035] The mode of monomers addition, reaction conditions and
agitator design were varied. Results showed that the pre-mixing
method using an organic solvent produced polyetherimide with the
lowest variability in its stoichiometry and therefore the most
homogeneous properties.
[0036] Solvent-free polymerization reactions were carried-out in a
glass reactor equipped with a mechanically agitator. The monomers
were 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride
(BPADA) and 1,3-phenylendiamine (mPD); and phthalic anhydride (PA)
was added as chain stopper. Total reactants mass was 50 grams
unless indicated otherwise, and all reactions in this example were
formulated with a 0.5 molar percentage excess of anhydride and 2.7
mol % chain stopper.
[0037] In experiments using solid reactants the batch reactor tube
was charged with solid reactants, the reactor was assembled,
evacuated and refilled with nitrogen gas four times. The reaction
mixture was electrically heated to a temperature of 250.degree. C.
and maintained this temperature for 10 minutes while the pressure
was kept at 1013 mbar absolute. When the reactor content was fully
melted, 5 minutes after reaching 250.degree. C., the agitation was
started up and raised to 20 rpm. Then, temperature was increased to
350.degree. C. and maintained at this temperature for a total of 36
minutes to carry out the polymerization. The agitation was
sequentially raised to reach a maximum of 80 rpm and the pressure
was reduced to 1000 Pa to maintain these conditions for the last 22
minutes of reaction.
[0038] In experiments using pre-mixed monomer, 17.1 grams of mPD
was added to 150 milliliters (mL) of dichloromethane and mixed in
an ultrasonic bath until completely dissolved. 82.4 grams of BPADA
were suspended in 1.3 liters (L) of dichloromethane and mixed for
10 minutes in an ultrasonic bath. 0.72 grams of PA were suspended
in 50 milliliters (mL) of dichloromethane and mixed for 10 minutes
in an ultrasonic bath. The three mixtures were combined together to
have a total of 1.5 L. At this point, it was observed that an
exothermic reaction occurred. The mixture was stirred in an
ultrasonic bath for 2 hours at room temperature. The mixture was
then removed from the ultrasonic bath and the solvent was
evaporated in a rotovap at 50.degree. C. and 75,000 Pa. The
pressure was gradually reduced down to 30,000 Pa until no more
condensate was observed. The rotovap operation lasted a total of
2.5 hours per batch. The solid was left to dry overnight in a
vacuum oven at 30.degree. C. and 10,000 Pa of pressure. After the
procedure, a dry fine powder mix was obtained, ready to be charged
into the glass reactor tube. The solid was added to the reactor
tube and the melt polymerization was run as described in the
preceding paragraph. Examples 1B and 1D used the same conditions
and method.
[0039] Homogeneity of the polyetherimide was determined with the
analysis of final stoichiometry by Fourier-transform Infrared
Spectrometry (FTIR) in five different points of the final polymer
mass. A negative stoichiometry indicates a polyetherimide which has
an excess of amine end groups whereas a positive stoichiometry
indicates a polyetherimide which has an excess of anhydride end
groups. The pre-mixing of reactants using a volatile organic
solvent resulted in a standard deviation below 0.1 mol %, as shown
in Table 1. This is in comparison to the rest of the modifications
which resulted in a standard deviation greater than or equal to
0.87 mol %.
TABLE-US-00001 TABLE 1 Standard Average deviation of Reactant Max
agitator stoichiometry of stoichiometry mass (g) Mode of addition
speed (rpm) polymer (mol %) (mol %) A* 50 Solid monomers 80 -1.74
1.45 B 50 Pre-mixing method 80 -1.01 0.05 C* 50 Solid monomers 10
-0.55 2.08 D 50 Pre-mixing method 80 -1.18 0.09 E* 30 Solid
monomers 80 -1.59 0.87 *Comparative
Example 2
[0040] Three different reaction conditions were used to verify
whether the "cement stage" transition occurred using the pre-mixing
method and to characterize the properties of the polymer during
this "cement stage". This was achieved by stopping the reaction at
intermediates states. It was concluded that the pre-mixing method
eliminated the presence of the "cement stage" during the batch
solvent-free polymerization of polyetherimide.
[0041] Procedure A (Comparative)
[0042] Solvent-free polymerization reactions were carried-out in a
glass reactor equipped with a mechanical agitator. The monomers and
chain stopper were charged as solids in the reactor tube and mixed
with a metal rod prior to assembling the reactor. A total of 5
reactions were performed using this procedure with the objective of
isolating the intermediate stages and study the time-evolution of
the polymerization reaction. Therefore, the same procedure was
followed for all experiments, but the reactions were stopped,
cooled and analyzed at different reaction times.
[0043] A total reactants mass of 50 grams was charged in the
reactor tube, and it was formulated at 0.5 molar percentage excess
amine and 3.0% chain stopper. After the tube was charged with solid
reactants and mixed with a metal rod, the reactor was assembled,
evacuated and refilled with nitrogen gas four times. The reaction
mixture was electrically heated to a temperature of 225.degree. C.
and maintained this temperature for 10 minutes while the pressure
was kept at 101,300 Pa. When the reactor content was fully melted,
5 minutes after reaching 225.degree. C., the agitation was started
up and raised to 20 rpm. Then, temperature was increased to
350.degree. C. and maintained at this temperature for a total of 30
minutes to carry out the polymerization at atmospheric pressure.
The agitation was sequentially raised to reach 80 rpm three minutes
after the reactor temperature reached 350.degree. C. and maintained
for 12 minutes. Then, agitation speed was raised to maintain a
maximum of 100 rpm in the last 15 minutes of reaction. The
reactions were stopped at intermediate stages, as indicated by the
solid bars in FIG. 1.
[0044] The "cement stage" was isolated in the reaction which was
stopped 5 minutes after reaching 350.degree. C. (reaction II). The
molecular weight distribution was determined by GPC analysis for
all the reactions and is shown in FIG. 2. It was observed that the
"cement stage" had an abnormally high weight average molecular
weight (Mw) and polydispersity (PDI) compared with the
corresponding polymer mass in the early stages of the
polymerization.
[0045] Procedure B (Comparative)
[0046] Solvent-free polymerization reactions were carried-out in a
glass reactor equipped with a mechanically agitator. The monomers
and chain stopper were charged as solids in the reactor tube and
mixed with a metal rod prior to assembling the reactor. In this
procedure, the BPADA was melted before the experiment to eliminate
water and have better stoichiometry adjustment. A total of 5
reactions were performed with the objective of isolating the
intermediate stages and study the time-evolution of the
polymerization. Therefore, the same procedure was followed for all
experiments, but the reactions were stopped, cooled and analyzed at
different reaction times.
[0047] A total reactants mass of 50 grams was charged in the
reactor tube, and it was formulated at 0.5 molar percentage excess
anhydride and 2.7% chain stopper. After the tube was charged with
solid reactants and mixed with a metal rod, the reactor was
assembled, evacuated and refilled with nitrogen gas four times. The
reaction mixture was electrically heated to a temperature of
250.degree. C. and maintained this temperature for 10 minutes while
the pressure was kept at 101,300 Pa. When the reactor content was
fully melted, 5 minutes after reaching 250.degree. C., the
agitation was started up and raised to 20 rpm. Then, temperature
was increased to 350.degree. C. and maintained at this temperature
for a total of 126 minutes to carry out the polymerization. The
agitation was sequentially raised to reach a maximum of 80 rpm and
the pressure was reduced to 1000 Pa to maintain these conditions
for the last 112 minutes of reaction. The reactions were stopped at
intermediate stages, as indicated by the solid bars in FIG. 3.
[0048] The "cement stage" was observed in reactions I and II
stopped at 30 and 45 minutes of batch reaction time. The reaction
mixture was not homogeneous, as verified with measurement of
stoichiometry at different point of the reaction mass. The "cement
stage" showed an excess of anhydride groups. Therefore, it was
confirmed that the polymerization goes through a "cement stage"
when solid monomers are charged directly to the reactor. There were
two phases in the reaction mass, an amine rich phase at the bottom
of the reactor and an anhydride rich phase at the top of the
reactor tube, thus providing further evidence that monomers melting
at different temperatures produce a heterogeneous reaction
mixture.
[0049] Individual measurements of stoichiometry are shown in FIG. 4
and compared with a reaction performed at 300.degree. C. for a
total time of 90 minutes. The variability of the reaction mixture
was reduced with increasing temperature to 350.degree. C. and
extending reaction time. Stoichiometry measurement from 5 aliquots
in reaction IV showed a standard deviation of 0.45 mol %. This is a
large variability when compared to the standard deviations of less
than 0.1 mol percent in reactions using the pre-mixing method.
[0050] Procedure C
[0051] The monomers and chain stoppers were pre-mixed in an organic
solvent to produce a homogeneous powder mix, which was charged in
the glass reactor tube to carry out the solvent-free polymerization
reactions. A total of 4 reactions were performed with the objective
of isolating the intermediate stages and study the time-evolution
of the polymerization reaction. Therefore, the same procedure was
followed for all experiments, but the reactions were stopped,
cooled and analyzed at different reaction times
[0052] The mix of reactants was formulated at 1 molar percentage
excess anhydride and 2.2% chain stopper. A weighted amount of 17.3
grams of mPD was added to 150 mL of dichloromethane and mixed in an
ultrasonic bath until complete dissolution. A quantity of 84 grams
of BPADA were suspended in 1.3 L of dichloromethane and mixed for
10 minutes in an ultrasonic bath. A quantity of 0.49 grams of PA
were suspended in 50 mL of dichloromethane and mixed for 10 minutes
in an ultrasonic bath. Then, the three solutions were mixed
together to have a total of 1.5 L. At this point, it was observed
that an exothermic reaction occurred. The mixture was stirred in an
ultrasonic bath for 2 hours at room temperature. Later the solvent
was evaporated in a rotovap at 50.degree. C. and 75,000 Pa. The
pressure was gradually reduced down to 3000 Pa until no more
condensate was observed. The rotovap operation lasted a total of
2.5 hours per batch. Then, the solid was left to dry overnight in a
vacuum oven at 30.degree. C. and 10,000 Pa of pressure. After the
pre-mixing method, a dry fine powder mix was obtained, ready to be
charged into the glass reactor tube.
[0053] A total reactants mass of 45 grams was charged in the
reactor tube. After the charge was completed, the reactor was
assembled, evacuated and refilled with nitrogen gas four times. The
reaction mixture was electrically heated to a temperature of
250.degree. C. and maintained this temperature for 10 minutes while
the pressure was kept at 1013 mbar absolute. When the reactor
content was fully melted, 5 minutes after reaching 250.degree. C.,
the agitation was started up and raised to 20 rpm. Then,
temperature was increased to 350.degree. C. and maintained at this
temperature for a total of 36 minutes to carry out the
polymerization. The agitation was sequentially raised to reach a
maximum of 80 rpm and the pressure was reduced to 1,000 Pa to
maintain these conditions for the last 22 minutes of reaction.
Profiles of pressure, temperature and agitation speed during
polymerization are shown in FIG. 5, as indicated by the solid
bars.
[0054] No "cement stage" was observed in reactions stopped at 20
and 25 minutes of batch reaction time. The reaction mixtures were
homogeneous, as verified with measurement of stoichiometry at
different point of the reaction mass (see FIG. 6). Therefore, it
was confirmed that the pre-mixing method favors the homogeneous
melting of the reactants and eliminates the formation of the
"cement stage".
[0055] The standard deviation of stoichiometry is 0.06 mol % at the
end of polymerization using the pre-mixing method (Procedure C).
Comparison of this result to a standard deviation of 0.45 mol %
adding solid monomers (see FIG. 4) confirms that the pre-mixing
method produces a more homogeneous resin.
[0056] This disclosure further encompasses the following
embodiments.
Embodiment 1
[0057] A method of making a polyetherimide comprises forming a
monomer mixture comprising a bis(ether anhydride), a diamine and a
volatile organic solvent; removing the volatile organic solvent to
form a particulate solid; and melt polymerizing the particulate
solid at a temperature of 50 to 225.degree. C. higher than the
glass transition temperature of the polyetherimide in a single melt
mixing device to produce a polyetherimide having an anhydride-amine
stoichiometry and the standard deviation of anhydride-amine
stoichiometry is less than 0.4 mol %.
Embodiment 2
[0058] The method of Embodiment 1, wherein the monomer mixture is
formed by combining a bis(ether anhydride) mixture and a diamine
mixture, wherein the bis(ether anhydride) mixture comprises the
bis(ether anhydride) and the volatile organic solvent and the
diamine mixture comprises the diamine and the volatile organic
solvent.
Embodiment 3
[0059] The method of Embodiment 2, wherein the bis(ether anhydride)
mixture further comprises a chain stopper.
Embodiment 4
[0060] The method of Embodiment 2, wherein the diamine mixture
further comprises a chain stopper.
Embodiment 5
[0061] The method of any one of Embodiments 1 to 4, wherein at
least a portion of the melt polymerization is conducted at a
pressure below atmospheric pressure (760 mm Hg or 101,325 Pa).
Embodiment 6
[0062] The method of any one of Embodiments 1 to 5, wherein an
excess of bis(ether anhydride) relative to the diamine is used to
produce a polyetherimide having an excess of anhydride groups
relative to the amount of amine groups.
Embodiment 7
[0063] The method of any one of Embodiments 1 to 6, wherein the
volatile organic solvent comprises dichloromethane, acetone, or a
combination of the foregoing.
Embodiment 8
[0064] The method of any one of Embodiments 1 to 7, wherein melt
polymerizing occurs at a temperature 50 to 150.degree. C. greater
than the glass transition temperature of the polyetherimide.
Embodiment 9
[0065] The method of any one of Embodiment 1 to 8, wherein at least
a portion of the melt polymerization is conducted at a pressure
less than or equal to 5,000 Pa, or less than or equal to 1,000
Pa.
Embodiment 10
[0066] The method of any one of claims 1 to 9, wherein the
bis(ether anhydride) comprises
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride.
Embodiment 11
[0067] The method of any one of Embodiments 1 to 10, wherein the
diamine comprises m-phenylenediamine, p-phenylenediamine,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone,
3,3'-diaminodiphenyl sulfone, or a combination comprising at least
one of the foregoing.
Embodiment 12
[0068] The method of any one of the preceding Embodiments, wherein
the particulate solid has a solvent content less than or equal to
1000 ppm, or less than or equal to 100 ppm.
Embodiment 13
[0069] A melt polymerized polyetherimide having anhydride-amine
stoichiometry wherein the standard deviation of anhydride-amine
stoichiometry is less than 0.4 mol % and a solvent content less
than 50 ppm.
Embodiment 14
[0070] The polyetherimide of Embodiment 13, wherein the
polyetherimide has an anhydride-amine stoichiometry of -1 to 2.5
mol %.
Embodiment 15
[0071] The polyetherimide of Embodiment 13 or 14, wherein the
polyetherimide has a chlorine content less than or equal to 50 ppm,
or less than or equal to 25 ppm.
Embodiment 16
[0072] The polyetherimide of any one of Embodiments 13 to 15,
wherein the polyetherimide has a change in melt viscosity of less
than or equal to 50%, less than or equal to 40%, less than or equal
to 30%, or less than or equal to 20% after being maintained for 30
minutes at 390.degree. C. wherein melt viscosity is determined by
ASTM D4440.
Embodiment 17
[0073] The polyetherimide of any one of Embodiments 13 to 16
comprising structural units derived from
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and one
or more diamines comprising m-phenylenediamine, p-phenylenediamine,
4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, or
3,3'-diaminodiphenyl sulfone.
[0074] The compositions, methods, and articles can alternatively
comprise, consist of, or consist essentially of, any appropriate
materials, steps, or components herein disclosed. The compositions,
methods, and articles can additionally, or alternatively, be
formulated so as to be devoid, or substantially free, of any
materials (or species), steps, or components, that are otherwise
not necessary to the achievement of the function or objectives of
the compositions, methods, and articles.
[0075] All ranges disclosed herein are inclusive of the endpoints,
and the endpoints are independently combinable with each other
(e.g., ranges of "up to 25 wt. %, or, more specifically, 5 wt. % to
20 wt. %", is inclusive of the endpoints and all intermediate
values of the ranges of "5 wt. % to 25 wt. %," etc.).
"Combinations" is inclusive of blends, mixtures, alloys, reaction
products, and the like. The terms "first," "second," and the like,
do not denote any order, quantity, or importance, but rather are
used to distinguish one element from another. The terms "a" and
"an" and "the" do not denote a limitation of quantity, and are to
be construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by context. "Or"
means "and/or" unless clearly stated otherwise. Reference
throughout the specification to "some embodiments", "an
embodiment", and so forth, means that a particular element
described in connection with the embodiment is included in at least
one embodiment described herein, and may or may not be present in
other embodiments. In addition, it is to be understood that the
described elements may be combined in any suitable manner in the
various embodiments.
[0076] Unless specified to the contrary herein, all test standards
are the most recent standard in effect as of the filing date of
this application, or, if priority is claimed, the filing date of
the earliest priority application in which the test standard
appears.
[0077] Unless defined otherwise, technical and scientific terms
used herein have the same meaning as is commonly understood by one
of skill in the art to which this application belongs. All cited
patents, patent applications, and other references are incorporated
herein by reference in their entirety. However, if a term in the
present application contradicts or conflicts with a term in the
incorporated reference, the term from the present application takes
precedence over the conflicting term from the incorporated
reference.
[0078] Compounds are described using standard nomenclature. For
example, any position not substituted by any indicated group is
understood to have its valency filled by a bond as indicated, or a
hydrogen atom. A dash ("-") that is not between two letters or
symbols is used to indicate a point of attachment for a
substituent. For example, --CHO is attached through carbon of the
carbonyl group.
[0079] As used herein, the term "hydrocarbyl" includes groups
containing carbon, hydrogen, and optionally one or more heteroatoms
(e.g., 1, 2, 3, or 4 atoms such as halogen, O, N, S, P, or Si).
"Alkyl" means a branched or straight chain, saturated, monovalent
hydrocarbon group, e.g., methyl, ethyl, i-propyl, and n-butyl.
"Alkylene" means a straight or branched chain, saturated, divalent
hydrocarbon group (e.g., methylene (--CH.sub.2--) or propylene
(--(CH.sub.2).sub.3--)). "Alkenyl" and "alkenylene" mean a
monovalent or divalent, respectively, straight or branched chain
hydrocarbon group having at least one carbon-carbon double bond
(e.g., ethenyl (--HC.dbd.CH.sub.2) or propenylene
(--HC(CH.sub.3).dbd.CH.sub.2--). "Alkynyl" means a straight or
branched chain, monovalent hydrocarbon group having at least one
carbon-carbon triple bond (e.g., ethynyl). "Alkoxy" means an alkyl
group linked via an oxygen (i.e., alkyl-O--), for example methoxy,
ethoxy, and sec-butyloxy. "Cycloalkyl" and "cycloalkylene" mean a
monovalent and divalent cyclic hydrocarbon group, respectively, of
the formula --C.sub.nH.sub.2n-x and --C.sub.nH.sub.2n-2x-- wherein
x is the number of cyclization(s). "Aryl" means a monovalent,
monocyclic or polycyclic aromatic group (e.g., phenyl or naphthyl).
"Arylene" means a divalent, monocyclic or polycyclic aromatic group
(e.g., phenylene or naphthylene). "Arylene" means a divalent aryl
group. "Alkylarylene" means an arylene group substituted with an
alkyl group. "Arylalkylene" means an alkylene group substituted
with an aryl group (e.g., benzyl). The prefix "halo" means a group
or compound including one more halogen (F, Cl, Br, or I)
substituents, which can be the same or different. The prefix
"hetero" means a group or compound that includes at least one ring
member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms, wherein
each heteroatom is independently N, O, S, or P.
[0080] "Substituted" means that the compound or group is
substituted with at least one (e.g., 1, 2, 3, or 4) substituents
instead of hydrogen, where each substituent is independently nitro
(--NO.sub.2), cyano (--CN), hydroxy (--OH), halogen, thiol (--SH),
thiocyano (--SCN), C.sub.1-6 alkyl, C.sub.2-6 alkenyl, C.sub.2-6
alkynyl, C.sub.1-6 haloalkyl, C.sub.1-9 alkoxy, C.sub.1-6
haloalkoxy, C.sub.3-12 cycloalkyl, C.sub.5-18 cycloalkenyl,
C.sub.6-12 aryl, C.sub.7-13 arylalkylene (e.g, benzyl), C.sub.7-12
alkylarylene (e.g, toluyl), C.sub.4-12 heterocycloalkyl, C.sub.3-12
heteroaryl, C.sub.1-6 alkyl sulfonyl (--S(.dbd.O).sub.2-alkyl),
C.sub.6-12 arylsulfonyl (--S(.dbd.O).sub.2-aryl), or tosyl
(CH.sub.3C.sub.6H.sub.4SO.sub.2--), provided that the substituted
atom's normal valence is not exceeded, and that the substitution
does not significantly adversely affect the manufacture, stability,
or desired property of the compound. When a compound is
substituted, the indicated number of carbon atoms is the total
number of carbon atoms in the group, including those of the
substituent(s).
[0081] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or may be presently unforeseen may
arise to applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they may be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
* * * * *